Abstract
An attempt has been made to obtain direct evidence of electrochemical redox reaction, i.e. electronically mediated reaction (EMR) during TiCl4 reduction by magnesium, and it includes a clear understanding of the mechanism of titanium deposition in the Kroll process. Feed material of TiCl4 and reductant magnesium were charged into different locations in molten MgCl2 at 1073 K. Large current, more than 5 A, between these feed and reductant locations has been clearly detected when shortening these electronically isolated sites, and metallic titanium deposits were observed in the TiCl4 feed site. Reproducibility of these experiments was well-confirmed. Thus, magnesiothermic reduction of TiCl4 appears to occur by EMR without direct physical contact between feed and reductant. The usefulness of the concept of EMR was demonstrated by explaining mechanism of titanium deposition in the sponge form on the reactor wall and reaction pathways including the crawling behavior of magnesium on the metallic wall surface in the Kroll process. The present results suggest the concept of EMR plays an important roll in metallothermic reduction of TiCl4 due to electron transfer through an electronically conductive medium, e.g. reaction wall and titanium deposit and due to ion transfer through MgCl2 as an ionic conductive medium.
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